CN112126031A - Synthesis method of melamine formaldehyde resin in low-carbon alcohol system - Google Patents
Synthesis method of melamine formaldehyde resin in low-carbon alcohol system Download PDFInfo
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- CN112126031A CN112126031A CN202011124779.XA CN202011124779A CN112126031A CN 112126031 A CN112126031 A CN 112126031A CN 202011124779 A CN202011124779 A CN 202011124779A CN 112126031 A CN112126031 A CN 112126031A
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- reaction
- melamine
- heating
- resin
- formaldehyde resin
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- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 16
- 238000001308 synthesis method Methods 0.000 title description 2
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 16
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 13
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 13
- 230000001105 regulatory effect Effects 0.000 claims abstract description 10
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 abstract description 21
- 239000011347 resin Substances 0.000 abstract description 21
- 239000007787 solid Substances 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 8
- 238000004132 cross linking Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 11
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
- C08G12/42—Chemically modified polycondensates by etherifying
- C08G12/424—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds
- C08G12/425—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds based on triazines
- C08G12/427—Melamine
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a method for synthesizing melamine formaldehyde resin in a low-carbon alcohol system. The method comprises the following steps: adding paraformaldehyde into low-carbon alcohol, stirring and heating; regulating the pH value of the system to 7.5-8.0 by using triethanolamine, adding melamine, and heating for reaction, wherein the feeding weight ratio of the melamine, the paraformaldehyde and the low-carbon alcohol is 1: 1.4-2.0: 1.6-2.7; cooling, regulating the pH value of the system to 9.5-10.5 by using triethanolamine, and heating for continuous reaction; cooling, terminating the reaction and discharging. The invention is carried out in an anhydrous system, thereby ensuring the high solid content of the resin of the product; the polymerization reaction is carried out under the alkalescent condition, the reaction activity is not high, the speed is slow, the gel is not easily generated by overlarge crosslinking, and the reaction controllability is improved; the alcoholic hydroxyl group is used for etherifying the hydroxymethyl group in the resin to properly block the activity of the resin, so that the storage stability of the product resin is greatly improved.
Description
Technical Field
The invention relates to a method for synthesizing melamine formaldehyde resin, in particular to a method for synthesizing melamine formaldehyde resin in a low-carbon alcohol system.
Background
The melamine formaldehyde resin is a polymer obtained by reacting melamine with formaldehyde, is colorless, transparent, viscous and liquid, and is a synthetic resin widely used as a leather retanning agent, a papermaking wet strengthening agent, a coating adhesive, a fabric finishing agent and the like. The existing synthesis process comprises the following steps: the method comprises two steps of alkaline addition and acidic polymerization, namely, the addition reaction of melamine and formaldehyde is carried out under the alkalescent condition, and then the polymerization reaction of the generated methylol melamine is carried out under the acidic condition.
Although there are more relevant technologies, there are some problems that limit their application, including: 1) the materials are mainly 37% formaldehyde aqueous solution, acid or alkali solution, and more water is introduced, so that the solid content of the resin of the product is lower than 60%; 2) the hydroxymethyl melamine is subjected to polymerization reaction under an acidic condition, the hydroxyl in the hydroxymethyl becomes abnormally active due to the existence of hydrogen ions, the reaction process is fast, excessive crosslinking is easy to generate gel, and the control difficulty is high; 3) the resin molecules contain hydroxymethyl with higher reaction activity, and further crosslinking is easy to occur in the storage process, and the stability of the resin is reduced because the resin is gradually flocculated to gel. US-a 3520715 and US-a 3650821 both describe a process for the preparation of melamine formaldehyde resins by refluxing a mixture of melamine and an aqueous formaldehyde solution in an alkaline medium, the former being difficult to control and the product resin being prone to flocculation and sedimentation; the latter product resins can only last for approximately 12 hours. DE 3104420A1 describes a method for preparing melamine-formaldehyde resin by mixing and reacting melamine and formaldehyde aqueous solution with an optimal regulator at a temperature of 105-160 ℃ and under corresponding high pressure, but the stability of the product resin is poor.
Disclosure of Invention
In order to overcome the problems of low solid content and poor storage stability of the product resin in the prior art, the invention aims to provide a method for synthesizing melamine formaldehyde resin in a low-carbon alcohol system, so that the high solid content of the product resin is ensured; the reaction activity is not high, the speed is slow, the gel is not easily generated due to overlarge crosslinking, and the reaction controllability is improved; greatly improves the storage stability of the product resin.
The purpose of the invention is realized by the following technical scheme:
a method for synthesizing melamine formaldehyde resin in a low-carbon alcohol system is characterized by comprising the following steps:
1) adding paraformaldehyde into low-carbon alcohol, stirring and heating;
2) regulating the pH value of the system to 7.5-8.0 by using triethanolamine, adding melamine, and heating for reaction, wherein the feeding weight ratio of the melamine, the paraformaldehyde and the low-carbon alcohol is 1: 1.4-2.0: 1.6-2.7;
3) cooling, regulating the pH value of the system to 9.5-10.5 by using triethanolamine, and heating for continuous reaction;
4) cooling, terminating the reaction and discharging.
Further, the stirring and heating in the step 1) comprises: stirring at 160-170 r/min, heating to 60-70 ℃, and keeping the temperature for 20-40 min.
Further, in the step 1), the lower alcohol is any one of diethylene glycol, a mixture of diethylene glycol and ethylene glycol or methanol, and the mixing weight ratio of diethylene glycol and ethylene glycol or methanol is preferably 1.6-2.1: 1.
The heating reaction in the step 2) comprises the following steps: heating to 80-85 ℃, and reacting at constant temperature for 25-45 min.
Further, the feeding weight ratio of the melamine, the paraformaldehyde and the low carbon alcohol in the step 2) is preferably 1: 1.7-1.8: 2.1-2.5.
The step 3) of cooling comprises cooling to 50-60 ℃.
The heating reaction in the step 3) comprises the following steps: heating to 95-100 ℃, and reacting at constant temperature for 2.0-2.5 h.
Compared with the prior art, the invention has the beneficial effects that:
1) paraformaldehyde solid is used for replacing a formaldehyde solution, low-carbon alcohol is used for replacing water as a solvent, triethanolamine is used for replacing an alkali solution as a pH regulator, and water is not introduced, so that the high solid content of the product resin is ensured;
2) the hydroxymethyl melamine is subjected to polymerization reaction under the alkalescent condition, the reaction condition is mild, the hydroxymethyl activity is reduced, the speed is slow, and the gel is not easily generated due to excessive crosslinking, so that the reaction is more controllable and is less influenced by temperature fluctuation;
3) hydroxyl in low-carbon alcohol is used for etherifying hydroxymethyl in the resin to properly seal the activity of the resin, so that the resin is effectively prevented from further crosslinking, becoming sticky and flocculating in the storage process, and the storage stability of the product resin is improved.
Detailed Description
The invention will now be further illustrated by the following examples:
example 1
Sequentially adding 100g of diethylene glycol and 80g of paraformaldehyde into a 500ml four-neck flask, starting a stirrer, adjusting to 160r/min, heating to 65 ℃, and keeping the temperature for 35 min; regulating the pH value to 8.0 by using triethanolamine, adding 46g of melamine, heating to 82 ℃, and reacting at constant temperature for 30 min; cooling to 60 ℃, adjusting the pH value to 10.2 by using triethanolamine, continuously heating to 98 ℃, and reacting for 2.0 hours at constant temperature; cooling to 45 deg.c, terminating the reaction and discharging.
Example 2
Adding 80g of diethylene glycol, 38g of ethylene glycol and 80g of paraformaldehyde into a 500ml four-neck flask in sequence, starting a stirrer, adjusting to 170r/min, heating to 70 ℃, and keeping the temperature for 40 min; regulating the pH value to 7.8 by using triethanolamine, adding 46g of melamine, heating to 82 ℃, and reacting at constant temperature for 40 min; cooling to 55 ℃, adjusting the pH value to 10.5 by using triethanolamine, continuously heating to 100 ℃, and reacting for 2.5 hours at constant temperature; cooling to 42 deg.c, terminating the reaction and discharging.
Example 3
Sequentially adding 60g of diethylene glycol, 36g of ethylene glycol and 80g of paraformaldehyde into a 500ml four-neck flask, starting a stirrer, adjusting to 160r/min, heating to 68 ℃, and keeping the temperature for 20 min; regulating the pH value to 7.5 by using triethanolamine, adding 45g of melamine, heating to 85 ℃, and reacting for 25min at constant temperature; cooling to 52 ℃, adjusting the pH value to 9.9 by using triethanolamine, continuously heating to 95 ℃, and reacting for 2.0 hours at constant temperature; cooling to 45 deg.c, terminating the reaction and discharging.
Example 4
Adding 61g of diethylene glycol, 36g of methanol and 80g of paraformaldehyde into a 500ml four-neck flask in sequence, starting a stirrer, adjusting to 165r/min, heating to 70 ℃, and keeping the temperature for 30 min; regulating the pH value to 8.0 by using triethanolamine, adding 45g of melamine, heating to 80 ℃, and reacting at constant temperature for 35 min; cooling to 58 ℃, adjusting the pH value to 10.5 by using triethanolamine, continuously heating to 96 ℃, and reacting for 2.0 hours at constant temperature; cooling to 43 deg.c, terminating the reaction and discharging.
The materials used in the above examples and their weight ratios, the solids content of the product resin, and the storage stability results are summarized in Table 1.
The solids contents mentioned in Table 1 were determined according to GB/T2793-1995.
The storage stability referred to in Table 1 is the time elapsed from the start of discharge to the onset of clouding of the product resin. Table 1:
Claims (8)
1. a method for synthesizing melamine formaldehyde resin in a low-carbon alcohol system is characterized by comprising the following steps:
adding paraformaldehyde into low-carbon alcohol, stirring and heating;
regulating the pH value of the system to 7.5-8.0 by using triethanolamine, adding melamine, and heating for reaction, wherein the feeding weight ratio of the melamine, the paraformaldehyde and the low-carbon alcohol is 1: 1.4-2.0: 1.6-2.7;
cooling, regulating the pH value of the system to 9.5-10.5 by using triethanolamine, and heating for continuous reaction;
cooling, terminating the reaction and discharging.
2. The method for synthesizing melamine formaldehyde resin under a lower alcohol system according to claim 1, wherein the step 1) of stirring and heating comprises: stirring at 160-170 r/min, heating to 60-70 ℃, and keeping the temperature for 20-40 min.
3. The method for synthesizing the melamine formaldehyde resin under the lower alcohol system according to claim 1, wherein the lower alcohol in the step 1) is any one of diethylene glycol, a mixture of diethylene glycol and ethylene glycol or methanol, and the mixing weight ratio of diethylene glycol to ethylene glycol or methanol is 1.6-2.1: 1.
4. The method for synthesizing melamine formaldehyde resin under a lower alcohol system according to claim 1, wherein the temperature-raising reaction in step 2) comprises: heating to 80-85 ℃, and reacting at constant temperature for 25-45 min.
5. The method for synthesizing the melamine-formaldehyde resin in the lower alcohol system according to claim 1, wherein the feeding weight ratio of the melamine, the paraformaldehyde and the lower alcohol in the step 2) is 1: 1.7-1.8: 2.1-2.5.
6. The method for synthesizing the melamine-formaldehyde resin in the lower alcohol system according to claim 1, wherein the step 3) of cooling comprises cooling to 50-60 ℃.
7. The method for synthesizing melamine formaldehyde resin under a lower alcohol system according to claim 1, wherein the temperature-raising reaction in step 3) comprises: heating to 95-100 ℃, and reacting at constant temperature for 2.0-2.5 h.
8. The method for synthesizing melamine formaldehyde resin under a lower alcohol system according to claim 1, wherein the step 4) of cooling termination reaction comprises: and cooling to 40-45 ℃ to terminate the reaction.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011124779.XA CN112126031A (en) | 2020-10-20 | 2020-10-20 | Synthesis method of melamine formaldehyde resin in low-carbon alcohol system |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011124779.XA CN112126031A (en) | 2020-10-20 | 2020-10-20 | Synthesis method of melamine formaldehyde resin in low-carbon alcohol system |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4408045A (en) * | 1981-03-31 | 1983-10-04 | Chemie Linz Aktiengesellschaft | Process for the preparation of partially etherified methylolmelamines |
| US20090121181A1 (en) * | 2005-12-09 | 2009-05-14 | Basf Se Patents And Trademarks And Licenses | Etherified melamine/formaldehyde condensates having a high solid content and low viscosity |
| CN103641970A (en) * | 2013-12-04 | 2014-03-19 | 中国林业科学研究院林产化学工业研究所 | Preparation method of high-solid-content melamino-formaldehyde-base resin |
-
2020
- 2020-10-20 CN CN202011124779.XA patent/CN112126031A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4408045A (en) * | 1981-03-31 | 1983-10-04 | Chemie Linz Aktiengesellschaft | Process for the preparation of partially etherified methylolmelamines |
| US20090121181A1 (en) * | 2005-12-09 | 2009-05-14 | Basf Se Patents And Trademarks And Licenses | Etherified melamine/formaldehyde condensates having a high solid content and low viscosity |
| CN103641970A (en) * | 2013-12-04 | 2014-03-19 | 中国林业科学研究院林产化学工业研究所 | Preparation method of high-solid-content melamino-formaldehyde-base resin |
Non-Patent Citations (1)
| Title |
|---|
| 蔡正风 等: "无水醚化六羟甲基三聚氰胺树脂合成的新方法", 《化学世界》 * |
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Application publication date: 20201225 |